CN109355931B - Preparation method of multifunctional dyed fluorescent cotton fabric based on MOF - Google Patents

Preparation method of multifunctional dyed fluorescent cotton fabric based on MOF Download PDF

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CN109355931B
CN109355931B CN201811350520.XA CN201811350520A CN109355931B CN 109355931 B CN109355931 B CN 109355931B CN 201811350520 A CN201811350520 A CN 201811350520A CN 109355931 B CN109355931 B CN 109355931B
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cotton fabric
mof
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CN109355931A (en
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邢彦军
牛传文
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Donghua University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose

Abstract

The invention relates to a preparation method of a multifunctional dyed fluorescent cotton fabric based on MOF. The method comprises the following steps: preparing Zn-MOF pre-finished cotton fabric, and preparing multifunctional dyed fluorescent cotton fabric based on Zn-MOF. The method has simple process operation, high efficiency, no need of special equipment, low cost of raw materials, easy obtainment and suitability for industrial production; the prepared Zn-MOF-based multifunctional dyed fluorescent cotton fabric has excellent fluorescence performance, and simultaneously has various performances of antibiosis, deodorization, mildew and moth prevention, ultraviolet resistance, flame retardance and the like.

Description

Preparation method of multifunctional dyed fluorescent cotton fabric based on MOF
Technical Field
The invention belongs to the field of preparation of fluorescent cotton fabrics, and particularly relates to a preparation method of a multifunctional dyed fluorescent cotton fabric based on MOF.
Background
Fluorescent cotton fabrics as an important class of cotton fabric products have very important significance for enriching the variety of the cotton fabrics. At present, the common fluorescent fabric products are basically chemical fiber products, such as terylene, acrylon, chinlon and the like, and cotton fabrics with excellent fluorescent effect are rarely reported. Meanwhile, the fluorescent pigment for dyeing cotton fabrics in the market is mainly fluorescent paint. The cotton fabric dyed by the coating often has the problems of poor color fastness to rubbing and poor hand feeling, the problem can be well solved by selecting the fluorescent dye to dye the cotton fabric, the hand feeling of the fluorescent dye is superior to that of the fluorescent coating dyed cotton fabric, the fastness is excellent, but the fluorescent dye variety suitable for dyeing the cotton fabric is rare.
In recent years, Metal-Organic Frameworks (MOFs), especially Zn-MOFs, with high specific surface area and porosity have attracted much attention because of their properties of adjustable and controllable pore structure and size, ability to post-process materials, modifiable and tailorable structure, and easy functionalization. As a novel organic-inorganic hybrid material, MOFs (Metal organic frameworks) loaded on the surface of cotton fabrics by researchers (Cellulose,2012,19(5): 1771-1779; RSC Adv,2016,6(48): 42324-42333; Bioengineering,2018,5(1): 14; Ind Eng Chem Res,2018,57(28):9151-9161) show good application prospects. The MOF-loaded cotton fabric can be used in a plurality of fabric functional fields of antibiosis, deodorization, mildew and moth prevention, radiation protection, static resistance, ultraviolet resistance, wrinkle resistance, flame retardance, fluorescence and the like. Although the MOF-loaded cotton fabric has wide application prospect, the MOF-loaded cotton fabric also has some problems, such as poor mechanical property and mechanical stability caused by insufficient firm interface combination and the like. In addition, wrapping fluorescent dye or rare earth metal ions with excellent fluorescence property in MOF as a high-efficiency fluorescent sensor for sensing or detecting cations, anions, small molecules, steam, explosive substances and the like has become one of the main research directions of researchers (Chem-Eur J,2015,21(27): 9748-. However, as with most compounds, the use of powdered MOFs also suffers from poor melt-in-solution properties and poor processability. Therefore, how to overcome the problems has important practical value in developing a fluorescent cotton fabric which is dyed by the fluorescent dye based on the MOF and is efficient and stable.
Currently, the methods mainly adopted for synthesizing the MOF on the surface of the cotton fabric are as follows: solvent thermal synthesis, hydrothermal synthesis, microwave synthesis, ultrasonic synthesis, ionothermal synthesis, electrochemical synthesis, and mechanical synthesis (2018, Hebei Industrial science and technology, 35(1): 72-76).
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multifunctional dyed fluorescent cotton fabric based on MOF (metal organic framework), so as to overcome the defects of poor fluorescent effect, single light-emitting mode, poor mechanical property and mechanical stability between Zn-MOF and the cotton fabric and the like of the cotton fabric loaded with the metal organic framework compound in the prior art.
The invention innovatively provides that the fluorescent dye and rare earth metal ions are wrapped by Zn-MOF and efficiently loaded on the surface of the cotton fabric, the mutual synergistic effect between a subject and an object of a Zn-MOF composite structure is comprehensively utilized, the luminous efficiency of the cotton fabric is improved, the single luminous mode of the cotton fabric is changed, and meanwhile, the problem of poor mechanical property and mechanical stability between the fragile Zn-MOF and the flexible cotton fabric is effectively solved in a layer-by-layer self-assembly mode, so that the fluorescent dye is widely applied to the cotton fabric, and a novel preparation mode different from the traditional dyeing process is provided for the development of the fluorescent cotton fabric. According to the method, Zn-MOF is deposited on the surface of the cotton fabric in a layer-by-layer self-assembly mode, compared with other methods, the method is simple in equipment, low in reaction temperature and low in energy consumption, water is used as a solvent, and the difficulty in waste liquid treatment is low.
The invention discloses a Zn-MOF-based cotton fabric with multiple properties. The Zn-MOF-based multifunctional dyed fluorescent cotton fabric prepared by the invention has the traditional functional finishing characteristics of antibiosis, deodorization, mildew and moth prevention, ultraviolet resistance, flame retardance and the like, and the conventional color development and coloring performance, and also has good thermal stability, fluorescence stability, higher luminous efficiency and excellent fluorescence performance.
The invention discloses a preparation method of a multifunctional dyed fluorescent cotton fabric based on MOF, which comprises the following steps:
(1) pre-finishing cotton fabrics with a zinc salt aqueous solution and a polycarboxylic acid aqueous solution in sequence, and repeating the pre-finishing to obtain Zn-MOF pre-finished cotton fabrics, wherein the molar ratio of zinc salt to polycarboxylic acid is 1:1-1: 5;
(2) dipping and dyeing the pre-finished cotton fabric in the step (1) in a fluorescent dye solution, taking out the fabric for rinsing, airing to obtain a Zn-MOF dyed cotton fabric, dipping the cotton fabric in a rare earth salt water solution, taking out the fabric for washing, and drying to obtain a Zn-MOF based multifunctional dyed fluorescent cotton fabric;
or dipping the pre-finished cotton fabric in the step (1) in a rare earth salt solution, taking out the fabric, washing with water, drying to obtain a Zn-MOF-based fluorescent cotton fabric, dipping and dyeing the cotton fabric in a fluorescent dye solution, taking out the fabric, rinsing and airing to obtain a Zn-MOF-based multifunctional dyed fluorescent cotton fabric;
wherein the dosage of the fluorescent dye is 0.02-10.0% owf, and the concentration of the rare earth salt water solution is 0.001-0.1 mol/L.
The zinc salt in the step (1) is at least one of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate.
In the step (1), the polycarboxylic acid is at least one of terephthalic acid, trimesic acid, pyromellitic acid, 2-aminoterephthalic acid, 2, 5-dihydroxyterephthalic acid, 4-oxo-1, 4-dihydro-2, 6-pyridinedicarboxylic acid, pyridine-2, 6-dicarboxylic acid, succinic acid, glutaric acid, citric acid, butanetetracarboxylic acid and biphenyldicarboxylic acid.
The step (1) of pre-finishing the cotton fabric with a zinc salt aqueous solution and a polycarboxylic acid aqueous solution in sequence is as follows: soaking cotton fabric in zinc salt water solution, taking out the cotton fabric, washing with water, drying, soaking the cotton fabric in polycarboxylic acid solution, taking out the cotton fabric, washing with water, and drying, wherein the concentration of the zinc salt water solution is 0.2-1.2mol/L, and the concentration of the polycarboxylic acid water solution is 0.1-0.6 mol/L.
The dipping bath ratio is 1:5-1:50, the dipping temperature is 70-75 ℃, and the dipping time is 2-10 min.
The washing temperature is room temperature; the drying temperature is 80-120 deg.C, and the drying time is 10-30 min.
The number of times of repeating the pre-finishing in the step (1) is 1-16.
The process conditions of the pretreatment of the cotton fabric by the zinc salt aqueous solution and the pretreatment by the polycarboxylic acid aqueous solution in the step (1) are the same.
The fluorescent dye in the step (2) is at least one of rhodamine 6G, crystal violet, rhodamine B, acridine orange, safranin O, calcein and methylene blue; the solvent of the fluorescent dye solution is trichloromethane.
The rare earth salt in the step (2) is at least one of europium salt, samarium salt, terbium salt and dysprosium salt.
The europium salt is at least one of europium acetate, europium chloride, europium nitrate and europium sulfate.
The samarium salt is at least one of samarium acetate, samarium chloride, samarium nitrate and samarium sulfate.
The terbium salt is at least one of terbium acetate, terbium chloride, terbium nitrate and terbium sulfate.
The dysprosium salt is at least one of dysprosium acetate, dysprosium chloride, dysprosium nitrate and dysprosium sulfate.
In the step (2), the dip dyeing bath ratio is 1:5-1:50, the dip dyeing temperature is 20-40 ℃, and the dip dyeing time is 12-48 h.
The rinsing in the step (2) is carried out in trichloromethane.
In the step (2), the dipping bath ratio is 1:5-1:50, the dipping temperature is 20-40 ℃, and the dipping time is 6-24 h.
In the step (2), the drying temperature is 80-120 ℃, and the drying time is 10-45 min.
According to the invention, Zn-MOF can be uniformly loaded on the surface of the cotton fabric through a simple alternate cycle impregnation mode, so that the Zn-MOF cotton fabric has a wide application prospect in a plurality of fields, such as antibacterial, uvioresistant and flame retardant fields. In addition, since Zn-MOF has porosity and large specific surface area, a fluorescent dye and rare earth ions having excellent fluorescence properties can be introduced therein, thereby imparting new fluorescence characteristics thereto. The fluorescent dye and the rare earth ions are combined and introduced into Zn-MOF and loaded on the cotton fabric, the excellent fluorescent property can be endowed to the cotton fabric by utilizing the synergistic effect of the zinc ions, the polycarboxylic acid, the fluorescent dye and the rare earth ions, and the fluorescent dye can be applied to the fields of special clothing, anti-counterfeiting, detection, confidential materials and the like. Based on the principle, the invention provides the preparation method of the MOF-based multifunctional dyed fluorescent cotton fabric, which is simple and convenient to operate, low in raw material cost and easy to obtain, and suitable for large-scale production. In the preparation process, the cotton fabric is soaked in a zinc salt aqueous solution, the fabric is physically adsorbed and combined with zinc ions, then the fabric is soaked in a polycarboxylic acid aqueous solution under the same process condition with the zinc salt aqueous solution, the polycarboxylic acid and the zinc ions loaded on the surface of the fabric are complexed to form a compound with a specific framework structure and composition, and after the steps are repeated for a certain number of times, the Zn-MOF pre-finished cotton fabric is obtained in a layer-by-layer self-assembly mode. The method comprises the steps of dipping and dyeing Zn-MOF pre-finished cotton fabric at a certain temperature by trichloromethane dye liquor of fluorescent dye to obtain Zn-MOF dyed cotton fabric, and then dipping the dyed cotton fabric in rare earth salt water solution at a certain temperature (or dipping the Zn-MOF pre-finished cotton fabric in rare earth salt water solution at a certain temperature to obtain fluorescent cotton fabric based on Zn-MOF, and then dipping and dyeing the fluorescent cotton fabric in trichloromethane solution of fluorescent dye at a certain temperature.). After finishing, the fluorescent efficiency of the fluorescent cotton fabric can be further improved by utilizing the synergistic effect of the raw materials while endowing the cotton fabric with certain functions and colors, and finally the Zn-MOF-based multifunctional dyed fluorescent cotton fabric which is efficient, stable and durable and has the functions of antibiosis, deodorization, mildew and moth prevention, ultraviolet resistance and flame retardance is obtained. The preparation method is not limited to cotton fabrics, and the Zn-MOF-based multifunctional dyed fluorescent non-cotton fabric can be obtained by applying the method to the non-cotton fabric after certain treatment.
Advantageous effects
(1) According to the invention, the fluorescent dye and the rare earth ions are combined and introduced into Zn-MOF, and the luminous efficiency of the Zn-MOF-based multifunctional dyed fluorescent cotton fabric can be improved through the synergistic effect of the zinc ions, the polycarboxylic acid, the fluorescent dye and the rare earth ions.
(2) The zinc salt, the polycarboxylic acid and the rare earth salt used in the preparation process are nontoxic and harmless, the difficulty and the resource investment of waste liquid treatment are reduced, and the discharge of waste water is reduced.
(3) The preparation process has the advantages of simple operation, high production efficiency, no need of special equipment, low cost of raw materials, easy obtainment and suitability for industrial production.
(4) The Zn-MOF-based multifunctional dyed fluorescent cotton fabric prepared by the invention has multiple performances of antibiosis, deodorization, mildew and moth prevention, ultraviolet resistance, flame retardance and the like, and the performances can be well loaded on the cotton fabric by Zn-MOF, and the performances can still be maintained for a long time after washing and rubbing.
(5) The Zn-MOF-based multifunctional dyed fluorescent cotton fabric prepared by the invention is an excellent novel efficient fluorescent material, has good thermal stability, fluorescence stability and higher luminous efficiency, and can have a very good application prospect in the fields of special clothing, anti-counterfeiting, detection, confidential materials and the like.
(6) The invention is also applicable to other non-cotton type fabrics.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a Zn-MOF based multifunctional dyed fluorescent cotton fabric prepared in example 1.
FIG. 2 is an X-ray diffraction (XRD) pattern of the Zn-MOF based multifunctional dyed fluorescent cotton fabric prepared in example 1.
FIG. 3 is a fluorescence spectrum of multifunctional dyed fluorescent cotton fabric based on Zn-MOF prepared in example 1, with an excitation wavelength of 281nm (λ)ex＝281nm)。
FIG. 4 is a fluorescence spectrum of Zn-MOF based multifunctional dyed cotton fabric prepared in comparative example 3, with an excitation wavelength of 281nm (λ `)ex＝281nm)。
FIG. 5 is a fluorescence spectrum of Zn-MOF-based multifunctional fluorescent cotton fabric prepared in comparative example 4, with an excitation wavelength of 281nm (λ `)ex＝281nm)。
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Zinc acetate, zinc chloride, zinc nitrate, zinc sulfate, terephthalic acid, trimesic acid, pyromellitic acid, citric acid, butanetetracarboxylic acid, rhodamine 6G, crystal violet, rhodamine B, acridine orange, crocin O, chloroform, europium acetate, europium chloride, samarium chloride, terbium nitrate, dysprosium sulfate, and the like, which are used in the following examples, are commercially available.
Example 1
(1) Respectively preparing 0.8mol/L zinc acetate aqueous solution A and 0.4mol/L terephthalic acid aqueous solution B. Soaking the cotton fabric in the solution A at 70-75 ℃ for 5min, wherein the bath ratio is 1:50, washing with water at room temperature, and drying at 80 ℃ for 30 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 8 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing a trichloromethane solution C with 4.0% owf of rhodamine 6G, wherein the bath ratio is 1: and (3) dipping and dyeing the Zn-MOF pre-finished cotton fabric in the solution C for 48 hours at 50 and 20 ℃, taking out, rinsing in trichloromethane, and airing to obtain the Zn-MOF dyed cotton fabric. Preparing a 0.1mol/L europium acetate aqueous solution D, dipping the Zn-MOF dyed cotton fabric in the solution D for 12 hours at the temperature of 20 ℃, and taking out the fabric, wherein the bath ratio is 1: and 50, washing with water, and drying at 80 ℃ for 45min to obtain the Zn-MOF-based multifunctional dyed fluorescent cotton fabric. The Zn-MOF-based multifunctional dyed fluorescent cotton fabric has the bacteriostasis rate of more than 99% to staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, the fluorescence life is 1.023ms, the stability is good, the fluorescence quantum yield is 32.36 percent, the luminous efficiency is higher, the cotton fabric is changed into bright ruby red from light pink under the irradiation of ultraviolet light (281nm), and the cotton fabric is not changed after being stored in a dark place for 90 days, so that the application requirement can be met.
FIG. 1 shows that: the synthesized Zn-MOF uniformly covers the surface of the prepared dyed fluorescent cotton fabric, and the shape of the Zn-MOF is needle-shaped.
FIG. 2 shows that: the XRD pattern of the compound covered on the surface of the cotton fabric is consistent with that of Zn-MOF known in the literature, and the compound can be shown as the target product Zn-MOF.
FIG. 3 shows: the fluorescence spectrogram of the multifunctional dyed fluorescent cotton fabric based on Zn-MOF has strong absorption peaks at 589nm, 614nm, 649nm and 696nm, the absorption peaks are basically consistent with characteristic peaks of rhodamine 6G and europium acetate, and the positions of the absorption peaks are slightly shifted, wherein the characteristic peak of rhodamine 6G at about 580nm is influenced by the characteristic peak of europium acetate at about 593nm, so that the characteristic peaks of rhodamine 6G and europium acetate coincide to increase the intensities of the absorption peaks at 589nm and 696 nm.
Example 2
(1) Respectively preparing 0.6mol/L zinc chloride aqueous solution A and 0.4mol/L trimesic acid aqueous solution B. Soaking the cotton fabric in the solution A at 70-75 ℃ for 5min, wherein the bath ratio is 1:50, washing with water at room temperature, and drying at 90 ℃ for 25 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 8 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing a trichloromethane solution C with 2.0% owf of crystal violet, wherein the bath ratio is 1: and (3) dipping and dyeing the Zn-MOF pre-finished cotton fabric in the solution C for 36 hours at the temperature of 50 and 25 ℃, taking out, rinsing in trichloromethane, and airing to obtain the Zn-MOF dyed cotton fabric. Preparing a 0.05mol/L europium chloride aqueous solution D, dipping the Zn-MOF dyed cotton fabric in the solution D for 12 hours at 25 ℃, and taking out the fabric, wherein the bath ratio is 1: and 50, washing with water, and drying at 90 ℃ for 30min to obtain the Zn-MOF-based multifunctional dyed fluorescent cotton fabric. The Zn-MOF-based multifunctional dyed fluorescent cotton fabric has the bacteriostasis rate of more than 99% to staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, the fluorescence life is 1.002ms, the stability is good, the fluorescence quantum yield is 28.13%, the luminous efficiency is high, the cotton fabric is changed from light purple under the irradiation of ultraviolet light (281nm) into bright blue purple, the cotton fabric is not changed after being stored in a dark place for 90 days, and the application requirement can be met.
Example 3
(1) Respectively preparing 0.4mol/L zinc nitrate aqueous solution A and 0.1mol/L pyromellitic acid aqueous solution B. Soaking the cotton fabric in the solution A at 70-75 ℃ for 8min, wherein the bath ratio is 1: 20, washing with water at room temperature, and drying at 100 ℃ for 20 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 12 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing 0.01mol/L samarium chloride aqueous solution C, dipping the Zn-MOF pre-finished cotton fabric in the solution C for 18 hours at 30 ℃, and taking out the cotton fabric, wherein the bath ratio is 1: and (20) washing with water, and drying at 100 ℃ for 20min to obtain the Zn-MOF-based fluorescent cotton fabric. Preparing a trichloromethane solution D with 1.0% owf of rhodamine B, wherein the bath ratio is 1: and (3) dipping and dyeing the Zn-MOF-based fluorescent cotton fabric in the solution D for 24 hours at 20 and 30 ℃, then taking out, rinsing in chloroform, and airing to obtain the Zn-MOF-based multifunctional dyed fluorescent cotton fabric. The Zn-MOF-based multifunctional dyed fluorescent cotton fabric has the bacteriostasis rate of more than 99% to staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, the fluorescence life is 1.008ms, the stability is good, the fluorescence quantum yield is 30.18%, the luminous efficiency is high, and the cotton fabric can be stored in a dark place for 90 days without change, thereby meeting the application requirements.
Example 4
(1) 0.4mol/L zinc sulfate aqueous solution A and 0.2mol/L citric acid aqueous solution B are respectively prepared. Soaking the cotton fabric in the solution A at 70-75 ℃ for 8min, wherein the bath ratio is 1: 20, washing with water at room temperature, and drying at 100 ℃ for 20 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 12 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing a trichloromethane solution C with the acridine orange dosage of 0.5% owf, wherein the bath ratio is 1: and (3) dipping and dyeing the Zn-MOF pre-finished cotton fabric in the solution C for 18 hours at the temperature of 20 and 35 ℃, taking out, rinsing in trichloromethane, and airing to obtain the Zn-MOF dyed cotton fabric. Preparing a 0.01mol/L terbium nitrate water solution D, soaking the Zn-MOF dyed cotton fabric in the solution D for 15 hours at the temperature of 35 ℃, and taking out the fabric, wherein the bath ratio is 1: and (20) washing with water, and drying at 100 ℃ for 20min to obtain the Zn-MOF-based multifunctional dyed fluorescent cotton fabric. The Zn-MOF-based multifunctional dyed fluorescent cotton fabric has the bacteriostasis rate of more than 99% to staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, the fluorescence lifetime is 0.876ms, the stability is good, the fluorescence quantum yield is 27.96%, the luminous efficiency is high, and the cotton fabric can be stored in a dark place for 90 days without change, thereby meeting the application requirements.
Example 5
(1) Respectively preparing 0.2mol/L zinc nitrate aqueous solution A and 0.1mol/L butanetetracarboxylic acid aqueous solution B. Soaking the cotton fabric in the solution A at 70-75 ℃ for 10min, wherein the bath ratio is 1: 10, washing with water at room temperature, and drying at 120 ℃ for 10 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 16 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing 0.001mol/L dysprosium sulfate aqueous solution C, dipping the Zn-MOF pre-finished cotton fabric in the solution C for 24 hours at 40 ℃, and taking out the cotton fabric, wherein the bath ratio is 1: and 10, washing with water, and drying at 120 ℃ for 10min to obtain the Zn-MOF-based fluorescent cotton fabric. Preparing a trichloromethane solution D with safranine O dosage of 0.1% (owf), wherein the bath ratio is 1: and (3) dipping and dyeing the Zn-MOF-based fluorescent cotton fabric in the solution D at the temperature of 10 ℃ for 12 hours, taking out, rinsing in trichloromethane, and airing to obtain the Zn-MOF-based multifunctional dyed fluorescent cotton fabric. The Zn-MOF-based multifunctional dyed fluorescent cotton fabric has the bacteriostasis rate of more than 99% to staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, the fluorescence lifetime is 0.885ms, the stability is good, the fluorescence quantum yield is 28.04%, the luminous efficiency is higher, and the cotton fabric can be stored in a dark place for 90 days without change, thereby meeting the application requirements.
Comparative example 1
Preparing a trichloromethane solution A with 4.0% owf of rhodamine 6G, wherein the bath ratio is 1: and (3) dipping and dyeing the common cotton fabric in the solution A for 48 hours at 50 ℃ and 20 ℃, then taking out, rinsing in trichloromethane, and airing to obtain the dyed cotton fabric. The fastness to washing, dry rubbing and wet rubbing of the dyed cotton fabric is 3-4 grades, the limiting oxygen index LOI is 18, the fluorescence performance of the dyed cotton fabric is extremely poor, almost no fluorescence phenomenon exists, and the dyed cotton fabric is not changed after being stored for 90 days in a dark place.
Comparative example 2
Preparing 0.1mol/L europium acetate aqueous solution A, dipping a common cotton fabric in the solution A for 12 hours at the temperature of 20 ℃, and taking out the cotton fabric, wherein the bath ratio is 1:50, washing with water, and drying at 80 ℃ for 45min to obtain the rare earth salt treated cotton fabric. The fastness to washing, dry rubbing and wet rubbing of the rare earth salt treated cotton fabric is 3-4 grades, the limiting oxygen index LOI is 18, the fluorescence life is extremely short and is only 0.028ms, the stability is extremely poor, the fluorescence quantum yield is 1.79 percent, the luminous efficiency is extremely poor, and the rare earth salt treated cotton fabric is not changed after being stored for 90 days in a dark place.
Comparative example 3
(1) Respectively preparing 0.8mol/L zinc acetate aqueous solution A and 0.4mol/L terephthalic acid aqueous solution B. Soaking the cotton fabric in the solution A at 70-75 ℃ for 5min, wherein the bath ratio is 1:50, washing with water at room temperature, and drying at 80 ℃ for 30 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 8 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing a trichloromethane solution C with 4.0% owf of rhodamine 6G, wherein the bath ratio is 1: and (3) dipping and dyeing the Zn-MOF pre-finished cotton fabric in the solution C for 48 hours at 50 and 20 ℃, then taking out, rinsing in trichloromethane, and airing to obtain the Zn-MOF-based multifunctional dyed cotton fabric. The Zn-MOF-based multifunctional dyed cotton fabric has the bacteriostatic rate of more than 99 percent on staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, compared with the example 1, the fluorescent life is short and is only 0.198ms, the stability is poor, the fluorescent quantum yield is only 5.78%, the luminous efficiency is poor, the cotton fabric is changed from light pink under the irradiation of ultraviolet light (281nm) into bright blue-purple, and the cotton fabric is not changed after being stored in a dark place for 90 days.
FIG. 4 shows that: an absorption peak appears at 579nm in a fluorescence spectrogram of the multifunctional dyed cotton fabric based on Zn-MOF, which is basically consistent with a characteristic peak of common cotton fabric rhodamine 6G dyeing known in the literature, and the position of the absorption peak is slightly shifted, so that the rhodamine 6G and the Zn-MOF have a certain synergistic effect.
Comparative example 4
(1) Respectively preparing 0.8mol/L zinc acetate aqueous solution A and 0.4mol/L terephthalic acid aqueous solution B. Soaking the cotton fabric in the solution A at 70-75 ℃ for 5min, wherein the bath ratio is 1:50, washing with water at room temperature, and drying at 80 ℃ for 30 min; then dipping in the solution B under the same process conditions as the solution A, washing with water and drying. And repeating the steps for 8 times to obtain the Zn-MOF pre-finished cotton fabric.
(2) Preparing 0.1mol/L europium acetate aqueous solution C, dipping the Zn-MOF dyed cotton fabric in the solution C for 12 hours at 20 ℃, and taking out the fabric, wherein the bath ratio is 1: and 50, washing with water, and drying at 80 ℃ for 45min to obtain the Zn-MOF-based multifunctional fluorescent cotton fabric. The Zn-MOF-based multifunctional fluorescent cotton fabric has the bacteriostasis rate of more than 99 percent to staphylococcus aureus and escherichia coli, the ultraviolet resistance UPF is 50+, the fastness to washing, dry rubbing and wet rubbing is 4-5 grades, and the limiting oxygen index LOI is 21; the cotton fabric can resist the high temperature of more than 400 ℃, compared with the example 1, the fluorescent life is shorter, 0.499ms, the stability is poorer, the fluorescent quantum yield is 14.65 percent, the luminous efficiency is poorer, the cotton fabric is changed from light pink under the sunlight to dark purple under the irradiation of ultraviolet light (281nm), and the cotton fabric is not changed after being stored in a dark place for 90 days.
FIG. 5 shows that: the fluorescence spectrum of the multifunctional fluorescent cotton fabric based on Zn-MOF shows stronger absorption peaks at 587nm, 611nm, 648nm and 694nm, which are basically consistent with the characteristic peaks of europium acetate known in the literature, the positions of the peaks are slightly shifted, and compared with the figure 3, the intensity of the peaks is smaller, which indicates that the synergistic effect exists between the europium acetate and the Zn-MOF.

Claims (9)

1. A preparation method of a multifunctional dyed fluorescent cotton fabric based on MOF comprises the following steps:
(1) pre-finishing cotton fabrics with a zinc salt aqueous solution and a polycarboxylic acid aqueous solution in sequence, and repeating the pre-finishing to obtain Zn-MOF pre-finished cotton fabrics, wherein the molar ratio of zinc salt to polycarboxylic acid is 1:1-1: 5;
(2) dipping and dyeing the pre-finished cotton fabric in the step (1) in a fluorescent dye solution, taking out the fabric for rinsing, airing to obtain a Zn-MOF dyed cotton fabric, dipping the cotton fabric in a rare earth salt water solution, taking out the fabric for washing, and drying to obtain a Zn-MOF based multifunctional dyed fluorescent cotton fabric;
or dipping the pre-finished cotton fabric in the step (1) in a rare earth salt solution, taking out the fabric, washing with water, drying to obtain a Zn-MOF-based fluorescent cotton fabric, dipping and dyeing the cotton fabric in a fluorescent dye solution, taking out the fabric, rinsing and airing to obtain a Zn-MOF-based multifunctional dyed fluorescent cotton fabric;
wherein the dosage of the fluorescent dye is 0.02-10.0% owf, and the concentration of the rare earth salt water solution is 0.001-0.1 mol/L; the fluorescent dye is at least one of rhodamine 6G, crystal violet, rhodamine B, acridine orange and safranin O; the rare earth salt is at least one of europium salt, samarium salt, terbium salt and dysprosium salt; the europium salt is at least one of europium acetate, europium chloride, europium nitrate and europium sulfate; the samarium salt is at least one of samarium acetate, samarium chloride, samarium nitrate and samarium sulfate; the terbium salt is at least one of terbium acetate, terbium chloride, terbium nitrate and terbium sulfate; the dysprosium salt is at least one of dysprosium acetate, dysprosium chloride, dysprosium nitrate and dysprosium sulfate.
2. The method according to claim 1, wherein the zinc salt in the step (1) is at least one of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate; the polybasic carboxylic acid is at least one of terephthalic acid, trimesic acid, pyromellitic acid, 2-aminoterephthalic acid, 2, 5-dihydroxyterephthalic acid, 4-oxo-1, 4-dihydro-2, 6-pyridinedicarboxylic acid, pyridine-2, 6-dicarboxylic acid, succinic acid, glutaric acid, citric acid, butanetetracarboxylic acid and biphenyldicarboxylic acid.
3. The method according to claim 1, wherein the step (1) of pre-finishing the cotton fabric with the aqueous solution of the zinc salt and the aqueous solution of the polycarboxylic acid sequentially comprises the following specific steps: soaking cotton fabric in zinc salt water solution, taking out the cotton fabric, washing with water, drying, soaking the cotton fabric in polycarboxylic acid water solution, taking out the cotton fabric, washing with water, and drying, wherein the concentration of the zinc salt water solution is 0.2-1.2mol/L, and the concentration of the polycarboxylic acid water solution is 0.1-0.6 mol/L.
4. The method according to claim 3, wherein the dipping bath ratios are all 1:5-1:50, the dipping temperatures are all 70-75 ℃, and the dipping time is all 2-10 min.
5. The method of claim 3, wherein the water washing temperatures are all room temperature; the drying temperature is 80-120 deg.C, and the drying time is 10-30 min.
6. The method according to claim 1, characterized in that the process conditions of the pre-finishing of the cotton fabric with the zinc salt aqueous solution and the pre-finishing with the polycarboxylic acid aqueous solution in the step (1) are the same; the number of times of repeating the above pre-finishing is 1 to 16.
7. The method according to claim 1, wherein the solvent of the fluorescent dye solution in the step (2) is chloroform.
8. The method as claimed in claim 1, wherein the dip dyeing bath ratio in step (2) is 1:5-1:50, the dip dyeing temperature is 20-40 ℃, and the dip dyeing time is 12-48 h; the rinsing was carried out in chloroform.
9. The method according to claim 1, wherein the dipping bath ratios in the rare earth salt aqueous solution in the step (2) are respectively 1:5-1:50, the dipping temperatures in the rare earth salt aqueous solution are respectively 20-40 ℃, and the dipping time in the rare earth salt aqueous solution is respectively 6-24 h; the drying temperature is 80-120 deg.C, and the drying time is 10-45 min.
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